CN110152665A - CuO/Cu2The preparation method of O/Cu trielement composite material - Google Patents
CuO/Cu2The preparation method of O/Cu trielement composite material Download PDFInfo
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- CN110152665A CN110152665A CN201910456420.3A CN201910456420A CN110152665A CN 110152665 A CN110152665 A CN 110152665A CN 201910456420 A CN201910456420 A CN 201910456420A CN 110152665 A CN110152665 A CN 110152665A
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 134
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 38
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 8
- 210000005253 yeast cell Anatomy 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims description 3
- 208000011580 syndromic disease Diseases 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 46
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 238000005245 sintering Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000235342 Saccharomycetes Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/36—Biochemical methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention provides a kind of CuO/Cu2The preparation method of O/Cu trielement composite material, comprising the following steps: prepare copper salt solution and lye respectively；It takes yeast to be added to the water culture, is successively added into copper salt solution and lye after culture, obtain mixed liquor；Mixed liquor heating reaction obtains reaction solution；It will calcine and be cooled to room temperature after reaction solution drying, then calcine again, CuO/Cu can be obtained2O/Cu trielement composite material.Above-mentioned CuO/Cu2The preparation method of O/Cu trielement composite material as carbon source and can regulate and control presoma pattern during carbon thermal reduction synthesis using yeast as micro chemical reactor, simple process, and synthesis cycle is short.
Description
Technical field
The present invention relates to the preparation technical field of composite material, in particular to a kind of CuO/Cu2O/Cu trielement composite material
Preparation method.
Background technique
With getting worse for Ecological Environment Crisis, the heterogeneous composite material that can reduce environmental pollution is explored as letter at present
The hot spot of the area researches such as breath, electronics and photocatalysis.In the method for pollutant removal, photocatalytic degradation can be directly by pollution
Object is converted into carbon dioxide and water, with the obvious advantage.In Photocatalytic Degradation Process, irradiation bomb has the activity for improving catalyst
Important contribution.Traditional photo catalysis reactor mostly uses greatly expensive ultraviolet light source, consumes energy high, unstable, mechanical steady
It is qualitative it is low, service life is short, and be harmful to the human body, it is considered to be uneconomic light source；And use visible light or black light can
To save economic cost, particularly suitable for extensive operation.As it can be seen that finding and designing the organic transformation light of new visible optical drive
Catalyst has great importance.Copper oxide (CuO) and cuprous oxide (Cu2It O) is p-type semiconductor, band gap width is respectively
1.2eV~1.9eV and 2.0eV~2.2eV, has the characteristics that at low cost, resourceful and non-toxic, however its photocatalysis is living
Property and stability need to be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of CuO/Cu2The preparation method of O/Cu trielement composite material, it is existing to solve
The CuO/Cu prepared in technology2O/Cu trielement composite material is unable to satisfy the technical issues of photocatalysis performance requirement.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The present invention provides one kind the following steps are included: S1, respectively preparation copper salt solution and lye；S2, yeast is taken to be added
It is cultivated in water, is successively added after culture into the copper salt solution and the lye, obtains mixed liquor；S3, the mixed liquor add
Thermal response obtains reaction solution；S4, it will calcine and be cooled to room temperature after reaction solution drying, then calcine, can be obtained again
The CuO/Cu2O/Cu trielement composite material.
Further, in the step S2, the mass volume ratio of the yeast and water is 0.05g/ml~0.15g/ml, training
The concentration of yeast cells is 10 in solution after supporting6~107A/ml.
Further, the incubation time of the yeast in water is 30min~45min.
Further, in the step S3, the mixed liquor heating reaction is that the mixed liquor is placed in microwave reactor
Middle heating is reacted, and heating temperature is 70 DEG C~90 DEG C.
Further, the time of the mixed liquor heating reaction is 4min~8min.
Further, the ratio between substance withdrawl syndrome of the copper salt solution and the lye is 1:1~4.
Further, the step S4 specifically: by the reaction solution it is dry after 250 DEG C~350 DEG C calcining 0.5h~
1h is cooled to room temperature, and is then calcined 0.5h~1h again at 450 DEG C~550 DEG C, is obtained the CuO/Cu after cooling2O/Cu tri-
First composite material.
Further, the trielement composite material granular size that the preparation method is prepared is 50nm~100nm.
CuO/Cu provided by the invention2The preparation method of O/Cu trielement composite material cultivates yeast in water, allows yeast
Growth, bivalent cupric ion, which enters in yeast cells and reacts with alkali, generates presoma Kocide SD；Saccharomycete as microreactor,
It can control the concentration of reactant, control reaction compartment, particle growth is restricted；During calcining, cell wall can be with
Be converted to carbon and be wrapped in presoma surface, carry out carbothermic reduction reaction, and to the granule-morphology of the trielement composite material of generation and
Size is controlled.Above-mentioned preparation method is using yeast as micro chemical reactor, conduct during carbon thermal reduction synthesis
Carbon source simultaneously can regulate and control presoma pattern, simple process, and synthesis cycle is short.
Detailed description of the invention
Fig. 1 is the CuO/Cu that the embodiment of the present invention 1 is prepared2The X ray diffracting spectrum of O/Cu trielement composite material；
Fig. 2 is the CuO/Cu that the embodiment of the present invention 1 is prepared2The scanning electron microscopic picture of O/Cu trielement composite material；
Fig. 3 is the CuO/Cu that the embodiment of the present invention 2 is prepared2The X ray diffracting spectrum of O/Cu trielement composite material；
Fig. 4 is the CuO/Cu that the embodiment of the present invention 2 is prepared2The scanning electron microscopic picture of O/Cu trielement composite material；
Fig. 5 is the CuO/Cu that the embodiment of the present invention 3 is prepared2The X ray diffracting spectrum of O/Cu trielement composite material；
Fig. 6 is the CuO/Cu that the embodiment of the present invention 3 is prepared2The scanning electron microscopic picture of O/Cu trielement composite material；
Fig. 7 is the CuO/Cu that Examples 1 to 5 is prepared2It is organic that O/Cu trielement composite material is applied to photocatalytic degradation
The uv absorption spectra of object methylene blue, wherein first figure is not add CuO/Cu2The control of O/Cu trielement composite material
Group is used for the uv absorption spectra of photocatalytic degradation of organic matter methylene blue.
Specific embodiment
With reference to the accompanying drawing and specific embodiment the present invention is further described in more detail.
The present invention is in the outstanding young project (project approval number: 17B138) in the Education in Hunan Room and Hunan Province's natural science
It is completed under the subsidy of fund (project approval number: 2018JJ3251).
The present invention provides a kind of CuO/Cu2The preparation method of O/Cu trielement composite material, comprising the following steps: S1, divide
It Pei Zhi not copper salt solution and lye；S2, it takes yeast to be added to the water culture, is successively added into copper salt solution and lye after culture,
Obtain mixed liquor；S3, mixed liquor heating reaction obtain reaction solution；S4, it will calcine and be cooled to room temperature after reaction solution drying, then
It calcines again, CuO/Cu can be obtained2O/Cu trielement composite material.
There is good separation of charge structure in order to be made, and with visible light absorption and reactivity site
CuO/Cu2O/Cu trielement composite material, technical staff has done a large amount of research, for example combines one on the surface of trielement composite material
Kind surface plasma body resonant vibration co-catalyst, can effectively inhibit the compound of photo-generate electron-hole, greatly improve photocatalysis material
The energy conversion efficiency of material.CuO/Cu is synthesized using sol-gel method, chemical vapour deposition technique, phonochemistry method or hydro-thermal method2O,
CuO and Cu2The synergistic effect of O, the surface plasmon resonance effect of CuO/Cu2O photocatalyst surface Cu explain catalysis and live
The enhancing of property.Specific example has, Mosleh S, Rahimi M R, Ghaedi M, et al.Sonochemical-assisted
synthesis of CuO/Cu2O/Cu nanoparticles as efficient photocatalyst for
simultaneous degradation of pollutant dyes in rotating packed bed reactor:LED
illumination and central composite designoptimization[J].Ultrasonics
Sonochemistry, 2018,40:601-610, use copper acetate, ammonium hydroxide for raw material, deionized water is solvent, by sonicating
Method and nitrogen are heat-treated to have obtained CuO/Cu2O/Cu nano particle finds it with good photocatalysis performance；Zhao Y,
Zhang Y,Zhao H,et al.Epitaxial growth of hyperbranched Cu/Cu2O/CuO core-shell
nanowire heterostructures for lithium-ion batteries[J].Nano Research,2015,8
(8): 2763-2776 uses copper sulphate, sodium hydroxide, ethylenediamine and hydrazine for raw material, oil bath heating method and continuous oxidation technique system
Standby Cu/Cu2O/CuO core-shell structure copolymer nano wire hetero structure finds it with excellent lithium battery performance.But above-mentioned preparation Cu/Cu2O/
The method of CuO composite material requires greatly complex device or complicated technology, toxic raw materials and solvent, and yield is lower.
Yeast is a kind of simple unicellular fungi, it belongs to facultative anaerobic bacteria, can be given birth under aerobic and oxygen-free environment
It deposits, and yeast is cheap, easily survives.The basic boom of yeast cells is mainly cell wall, cytoplasm, cell membrane, thin
Five parts of karyon and vacuole, the eucaryotic cell structure of saccharomycete is simple, there is the reactor of many precisions in its inside, can occur very
More chemical reactions, the network of signal passed through in reactor, cell itself can be obtained by these reactions
The behavior for being suitble to reaction to occur finally is made in regulation.Finally enable to those less related to the physiological property of cell itself
Reaction can carry out in the cell, obtain the product of function admirable, yeast cells provides good reaction platform.
CuO/Cu provided by the invention2The preparation method of O/Cu trielement composite material cultivates yeast in water, allows yeast
Growth, bivalent cupric ion, which enters in yeast cells and reacts with alkali, generates presoma Kocide SD；Saccharomycete as microreactor,
It can control the concentration of reactant, control reaction compartment, particle growth is restricted；During calcining, cell wall can be with
Be converted to carbon and be wrapped in presoma surface, carry out carbothermic reduction reaction, and to the granule-morphology of the trielement composite material of generation and
Size is controlled.
The present invention prepares CuO/Cu by carbothermic method using yeast as micro chemical reactor and carbon source2O/Cu
Trielement composite material, yeast can regulate and control the pattern of presoma, and synthesis process is easy to operate, reproducible, yield is high, technique
Compared to the above simple, synthesis cycle is short.
Further, in step S2, the mass volume ratio of yeast and water is 0.05g/ml~0.15g/ml, solution after culture
The concentration of middle yeast cells is 106~107A/ml.The incubation time of yeast in water is 30min~45min.The present invention uses
Dried yeast powder is grown after cultivating in water, and shrivelled cell can also restore in dried yeast powder.Control the mass body of yeast and water
Concentration of the product than mainly controlling reaction raw materials.
Further, yeast is active dry yeast.
Further, in step S3, mixed liquor heating reaction is anti-for mixed liquor is placed in heating progress in microwave reactor
It answers, heating temperature is 70 DEG C~90 DEG C.Traditional heating means have temperature gradient, and heat is from outside to inside.The present invention uses microwave
Auxiliary heating, heat are generated by inside, and heating is quickly, uniformly, energy-efficient without temperature gradient, are easy to control, therefore can
Make precursor product epigranular.Further, the time of mixed liquor heating reaction is 4min~8min.Mixed liquor heating reaction
Time have an impact to the granule size of presoma Kocide SD.Reaction time is too long, and the granularity of Kocide SD is too big；When reaction
Between it is too short, cause reaction uneven, be not thorough.
Further, the ratio between substance withdrawl syndrome of copper salt solution and lye is 1:1~4.Bivalent cupric ion enters yeast
Generate presoma Kocide SD into the cell and with alkaline reaction.When mantoquita excess, part copper ion generates precipitate C u (OH)2；
When lye excess, Kocide SD precipitating is dissolved in lye and generates Cu (OH)4 2-.Above-mentioned two situations will affect to a certain extent
Yield.
Further, step S4 specifically:, in 250 DEG C~350 DEG C calcining 0.5h~1h, will be cooled to after reaction solution drying
Then room temperature calcines 0.5h~1h again at 450 DEG C~550 DEG C, obtains CuO/Cu after cooling2O/Cu trielement composite material.Instead
It is calcined after answering liquid dry at 250 DEG C~350 DEG C, it is therefore an objective to yeast be calcined and generate carbon and be wrapped in presoma surface；After cooling
It is calcined again at 450 DEG C~550 DEG C, it is therefore intended that sufficiently progress carbothermic reduction reaction, and exclude remaining carbon.
Further, the trielement composite material granular size that preparation method is prepared is 50nm~100nm.System of the present invention
Standby obtained CuO/Cu2O/Cu trielement composite material granular size about 50nm~100nm, in the case where not reuniting, by nanometer sheet
It is combined into nano flower-like structure.
Chemical reagent used in following embodiment is commercially available.Yeast is Angel TH high activity dried yeast powder.
Embodiment 1
CuO/Cu in the present embodiment2The preparation method of O/Cu trielement composite material the following steps are included:
S1, the analytically pure cupric sulfate pentahydrate (CuSO by 2.5g4〃5H2O it) is added in 20mL deionized water, is made
The copper-bath of 0.5mol/L concentration.The analytically pure sodium hydroxide of 0.8g is dissolved in 20mL deionized water and prepares 1.0mol/L
Sodium hydroxide solution.
S2,2.0g yeast powder is added in 20mL deionized water and cultivates 30min, be added into after culture to copper sulphate
In solution, then above-mentioned mixed solution is gradually added dropwise in sodium hydroxide aqueous slkali and obtains mixed liquor.
S3, the step S2 mixed liquor obtained is placed in microwave reactor, 5min is reacted at 80 DEG C of temperature and is reacted
Liquid.
S4, reaction solution is dried into 12h with the revolving speed centrifugation of 5000rpm and in 80 DEG C of drying boxes.After reaction solution is dry
To solid sample, it being fitted into crucible with cover after being ground and is put into resistance furnace, 300 DEG C of sintering soak 1h are cooled to room temperature, then
Secondary grinding.The sample that grinding obtains is again loaded into crucible with cover and is put into resistance furnace and carries out second of calcining, calcination temperature
It is 500 DEG C, sintering soak 1h is cooled to room temperature, and CuO/Cu can be obtained in grinding2O/Cu trielement composite material.CuO/Cu2O/Cu
The yield of trielement composite material is 59.6%.
By CuO/Cu made from the present embodiment2O/Cu trielement composite material carries out X-ray diffraction detection and scanning electron microscope inspection
It surveys, respectively refers to Fig. 1, Fig. 2.As seen from Figure 1, there are CuO, Cu in the composite material that the present embodiment is prepared2O and Cu
Three-phase, it was demonstrated that sample manufactured in the present embodiment is CuO/Cu2O/Cu trielement composite material.Available, the present embodiment system by Fig. 2
Standby obtained CuO/Cu2O/Cu trielement composite material has agglomeration, is to close because the amount of yeast is relatively fewer in presoma
It is poor at stage dispersion effect；It is less in the gas of calcination stage, generation, so stomata is few, reunite serious.
Embodiment 2
CuO/Cu in the present embodiment2The preparation method of O/Cu trielement composite material the following steps are included:
S1, the analytically pure cupric sulfate pentahydrate (CuSO by 2.5g4〃5H2O it) is added in 20mL deionized water, is made
The copper-bath of 0.5mol/L concentration.The analytically pure sodium hydroxide of 0.8g is dissolved in 20mL deionized water and prepares 1.0mol/L
Sodium hydroxide solution.
S2,2.5g yeast powder is added in 20mL deionized water and cultivates 40min, be added into after culture to copper sulphate
In solution, then above-mentioned mixed solution is gradually added dropwise in sodium hydroxide aqueous slkali and obtains mixed liquor.
S3, the step S2 mixed liquor obtained is placed in microwave reactor, 8min is reacted under temperature 70 C and is reacted
Liquid.
S4, reaction solution is dried into 12h with the revolving speed centrifugation of 5000rpm and in 80 DEG C of drying boxes.After reaction solution is dry
To solid sample, it being fitted into crucible with cover after being ground and is put into resistance furnace, 250 DEG C of sintering soak 1h are cooled to room temperature, then
Secondary grinding.The sample that grinding obtains is again loaded into crucible with cover and is put into resistance furnace and carries out second of calcining, calcination temperature
It is 450 DEG C, sintering soak 1h is cooled to room temperature, and CuO/Cu can be obtained in grinding2O/Cu trielement composite material.CuO/Cu2O/Cu
The yield of trielement composite material is 62.8%.
By CuO/Cu made from the present embodiment2O/Cu trielement composite material carries out X-ray diffraction detection and scanning electron microscope inspection
It surveys, respectively refers to Fig. 3, Fig. 4.As seen from Figure 3, there are CuO, Cu in the composite material that the present embodiment is prepared2O and Cu
Three-phase, it was demonstrated that sample manufactured in the present embodiment is CuO/Cu2O/Cu trielement composite material.Available, the present embodiment system by Fig. 4
Standby obtained CuO/Cu2The granular size of O/Cu trielement composite material is about 100nm, is combined into nanometer sheet first, then by nanometer
Piece is combined into the shape of recalling rose flower, is presented the structure of nano flower-like, the size of nanometer flower structure be about 600nm~
700nm。
Embodiment 3
CuO/Cu in the present embodiment2The preparation method of O/Cu trielement composite material the following steps are included:
S1, the analytically pure cupric sulfate pentahydrate (CuSO by 2.5g4·5H2O it) is added in 20mL deionized water, is made
The copper-bath of 0.5mol/L concentration.The analytically pure sodium hydroxide of 1.6g is dissolved in 20mL deionized water and prepares 2.0mol/L
Sodium hydroxide solution.
S2,3.0g yeast powder is added in 20mL deionized water and cultivates 45min, be added into after culture to copper sulphate
In solution, then above-mentioned mixed solution is gradually added dropwise in sodium hydroxide aqueous slkali and obtains mixed liquor.
S3, the step S2 mixed liquor obtained is placed in microwave reactor, 4min is reacted at 90 DEG C of temperature and is reacted
Liquid.
S4, reaction solution is dried into 12h with the revolving speed centrifugation of 5000rpm and in 80 DEG C of drying boxes.After reaction solution is dry
To solid sample, it being fitted into crucible with cover after being ground and is put into resistance furnace, 350 DEG C of sintering soak 0.5h are cooled to room temperature,
Regrinding.The sample that grinding obtains is again loaded into crucible with cover and is put into resistance furnace and carries out second of calcining, calcining temperature
Degree is 550 DEG C, and sintering soak 0.5h is cooled to room temperature, and CuO/Cu can be obtained in grinding2O/Cu trielement composite material.CuO/
Cu2The yield of O/Cu trielement composite material is 61.3%.
By CuO/Cu made from the present embodiment2O/Cu trielement composite material carries out X-ray diffraction detection and scanning electron microscope inspection
It surveys, respectively refers to Fig. 5, Fig. 6.As seen from Figure 5, there are CuO, Cu in the composite material that the present embodiment is prepared2O and Cu
Three-phase, it was demonstrated that sample manufactured in the present embodiment is CuO/Cu2O/Cu trielement composite material.Available, the present embodiment system by Fig. 6
Standby obtained CuO/Cu2The granular size of O/Cu trielement composite material is about 50nm~100nm, and there are agglomerations for particle, but
It is that packed structures are irregular.
Embodiment 4
CuO/Cu in the present embodiment2The preparation method of O/Cu trielement composite material the following steps are included:
S1, the analytically pure Copper dichloride dihydrate (CuCl by 1.7g2·2H2O it) is added in 20mL deionized water, is made
The copper chloride solution of 0.5mol/L concentration.The analytically pure potassium hydroxide of 1.12g is dissolved in 20mL deionized water and prepares 1.0mol/
The potassium hydroxide solution of L.
S2,3.0g yeast powder is added in 20mL deionized water and cultivates 45min, be added into after culture to copper chloride
In solution, then above-mentioned mixed solution is gradually added dropwise in potassium hydroxide aqueous slkali and obtains mixed liquor.
S3, the step S2 mixed liquor obtained is placed in microwave reactor, 5min is reacted at 80 DEG C of temperature and is reacted
Liquid.
S4, reaction solution is dried into 12h with the revolving speed centrifugation of 5000rpm and in 80 DEG C of drying boxes.After reaction solution is dry
To solid sample, it being fitted into crucible with cover after being ground and is put into resistance furnace, 300 DEG C of sintering soak 1h are cooled to room temperature, then
Secondary grinding.The sample that grinding obtains is again loaded into crucible with cover and is put into resistance furnace and carries out second of calcining, calcination temperature
It is 500 DEG C, sintering soak 1h is cooled to room temperature, and CuO/Cu can be obtained in grinding2O/Cu trielement composite material.CuO/Cu2O/Cu
The yield of trielement composite material is 55.9%.
Embodiment 5
CuO/Cu in the present embodiment2The preparation method of O/Cu trielement composite material the following steps are included:
S1, the analytically pure Gerhardite (Cu (NO by 2.416g3)2·3H2O it) is added in 20mL deionized water, system
Obtain the copper nitrate solution of 0.5mol/L concentration.The analytically pure potassium hydroxide of 1.12g is dissolved in 20mL deionized water and is prepared
The potassium hydroxide solution of 1.0mol/L.
S2,3.0g yeast powder is added in 20mL deionized water and cultivates 45min, be added into after culture to copper nitrate
In solution, then above-mentioned mixed solution is gradually added dropwise in potassium hydroxide aqueous slkali and obtains mixed liquor.
S3, the step S2 mixed liquor obtained is placed in microwave reactor, 5min is reacted at 80 DEG C of temperature and is reacted
Liquid.
S4, reaction solution is dried into 12h with the revolving speed centrifugation of 5000rpm and in 80 DEG C of drying boxes.After reaction solution is dry
To solid sample, it being fitted into crucible with cover after being ground and is put into resistance furnace, 300 DEG C of sintering soak 1h are cooled to room temperature, then
Secondary grinding.The sample that grinding obtains is again loaded into crucible with cover and is put into resistance furnace and carries out second of calcining, calcination temperature
It is 500 DEG C, sintering soak 1h is cooled to room temperature, and CuO/Cu can be obtained in grinding2O/Cu trielement composite material.CuO/Cu2O/Cu
The yield of trielement composite material is 60.8%.
The CuO/Cu that Examples 1 to 5 is prepared2O/Cu trielement composite material is applied to photocatalytic degradation of organic matter
Experiment.Experimental procedure is as follows: the CuO/Cu that Example 1~5 is prepared2Each 0.1g of O/Cu trielement composite material, respectively plus
Enter into the methylene blue solution of 20mL concentration 20mg/L, be packed into teat glass, and it is dense into each test tube to be separately added into 0.3mL
Degree is the hydrogen peroxide of 30wt%.Above-mentioned test tube is put into than bright BL-GHX-V light reaction device, the xenon lamp of 1kw is opened, into
Row light-catalyzed reaction.After illumination 40min, each test tube is put into a centrifuge, 5min is centrifuged with the speed of 13000r/min, use glue
Head dropper draws in test tube that supernatant is into cuvette, respectively on ultra-violet and visible spectrophotometer (day the island proper, UV-2501)
Measure its absorbance.Control group does not add CuO/Cu2O/Cu trielement composite material, other processes with it is as before.Embodiment 1
~5 and the optical absorption map of control group see Fig. 7, concrete outcome such as table 1:
The photodegradation rate of the different embodiments of table 1 and control group
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Control group |
| Degradation rate (%) | 99.33 | 99.60 | 99.63 | 99.02 | 99.36 | 33.23 |
The CuO/Cu that Examples 1 to 5 is prepared2O/Cu trielement composite material is applied to photocatalytic degradation of organic matter methylene
The photodegradation rate of base indigo plant such as table 1.In than bright BL-GHX-V light reaction device, after illumination 40min, Examples 1 to 5 preparation
CuO/Cu2The photodegradation rate of O/Cu trielement composite material is respectively 99.33%, 99.60%, 99.63%, 99.02% He
99.36%.And control group is without addition CuO/Cu2O/Cu trielement composite material only exists the methylene in the case of hydrogen peroxide
Blue degradation rate is only 33.23%.The embodiment proves CuO/Cu prepared by the present invention2O/Cu trielement composite material has preferable
Photocatalysis performance.
The above description is merely a specific embodiment, but simultaneously difference is limited to this to protection scope of the present invention, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Also, the technical solution between each embodiment of the present invention can be combined with each other, but
To be based on can be realized by those of ordinary skill in the art, when the combination of technical solution occur it is conflicting or can not
Will be understood that the combination of this technical solution is not present when realization, also not the present invention claims protection scope within.Therefore, originally
The protection scope of invention should be based on the protection scope of the described claims.
Claims (8)
1. a kind of CuO/Cu2The preparation method of O/Cu trielement composite material, it is characterised in that: the following steps are included:
S1, copper salt solution and lye are prepared respectively；
S2, it takes yeast to be added to the water culture, is successively added after culture into the copper salt solution and the lye, is mixed
Liquid；
S3, mixed liquor heating reaction obtain reaction solution；
S4, it will calcine and be cooled to room temperature after reaction solution drying, then calcine again, the CuO/Cu can be obtained2O/Cu
Trielement composite material.
2. CuO/Cu according to claim 12The preparation method of O/Cu trielement composite material, which is characterized in that the step
In S2, the mass volume ratio of the yeast and water is 0.05g/ml ~ 0.15g/ml, and the concentration of yeast cells is in solution after culture
106~107A/ml.
3. CuO/Cu according to claim 12The preparation method of O/Cu trielement composite material, which is characterized in that the yeast
Incubation time in water is 30min~45min.
4. CuO/Cu according to any one of claims 1 to 32The preparation method of O/Cu trielement composite material, feature exist
In, in the step S3, the mixed liquor heating reaction is reacted for the mixed liquor is placed in heating in microwave reactor,
Heating temperature is 70 DEG C~90 DEG C.
5. CuO/Cu according to claim 42The preparation method of O/Cu trielement composite material, which is characterized in that the mixing
The time of liquid heating reaction is 4min~8min.
6. CuO/Cu according to any one of claims 1 to 32The preparation method of O/Cu trielement composite material, feature exist
In the ratio between substance withdrawl syndrome of the copper salt solution and the lye is 1:1~4.
7. CuO/Cu according to any one of claims 1 to 32The preparation method of O/Cu trielement composite material, feature exist
In the step S4 specifically: it, in 250 DEG C~350 DEG C calcining 0.5h~1h, will be cooled to room temperature after reaction solution drying,
Then it calcines 0.5h~1h again at 450 DEG C~550 DEG C, obtains the CuO/Cu after cooling2O/Cu trielement composite material.
8. CuO/Cu according to any one of claims 1 to 32The preparation method of O/Cu trielement composite material, feature exist
In the trielement composite material granular size that the preparation method is prepared is 50nm~100nm.
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| CN114984953A (en) * | 2022-06-09 | 2022-09-02 | 陕西科技大学 | Preparation method of Cu/CuO electrocatalytic material loaded on carbon substrate |
| CN114984953B (en) * | 2022-06-09 | 2023-12-29 | 陕西科技大学 | Preparation method of Cu/CuO electrocatalytic material loaded on carbon matrix |
| CN116254567A (en) * | 2022-12-12 | 2023-06-13 | 兰州大学 | Nanocomposite and preparation method and application thereof |
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